O, o-dialkyl s-(1, 2-disubstituted hydrazino) phosphorothiolothionates



0,0-DIALKYL S-(l,2-DISUBSTITUTED HYDRA- ZINO) PHOSPHOROTHIOLOTHIONATES Richard L. McConnell and Harry W. Coover, Jr., Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application February 6, 1957 Serial No. 638,450

12 Claims. (Cl. 260461) This invention relates to new organophosphorus compounds and to a method for producing those compounds.

The organophosphorus compounds within the scope of this invention have the structural formula:

wherein R and R are lower alkyl radicals containing from 1 to 4 carbon atoms and R and R are selected from the group consisting of hydrogen, nitro, hydroxy, alkyl radicals having 1 to 4 carbon atoms, halogen,

and amido radicals having the formula H 0 ma. wherein R is an alkyl radical containing 1 to 4 carbon atoms.

The compounds Within the scope of this invention are prepared by reacting a dialkyl phosphorothiolothionate with an azo compound wherein a substituted or unsubstituted phenyl radical is attached to each of the nitrogen atoms. The reaction can be illustrated by the following equation wherein the azo compound is azobenzene:

amino, alkoxy containing 1 to 4 carbon atoms, phenyl The dialkyl phosphorothiolothionates that are employed to produce the compounds of this invention have the structural formula:

The dialkyl phosphorothiolothionates that are employed in practicing this invention are readily prepared by the reaction of phosphorus pentasulfide, P 8 with the appropriate aliphatic alcoho The azo compounds that are employed in. practicing this invention can be prepared 'by the reduction of an aromatic nitrocom- I Patented Dec. 23, 1958 pound in an alkaline medium as represented by the 01 lowing equation:

Alternatively, the azo compounds can be prepared by the reaction of a suitable nitroso compound with aniline or an aniline derivative.

To prepare the compounds of this invention, the reaction between the dialkyl phosphorothiolothionate and the azo compound can be carried out by the portion-wise addition of the azo compound to the dialkyl phosphorothiolothionate. However, any order of addition of the reactants can be used. It is preferable to use equimolar quantities of the reactants, but, if desired, an excess of either of the reactants can be used. The temperature employed for carrying out the reaction is within the range of -25 to 150 C. and the preferred temperature range is 25 to C. The reaction time is usually within a range of 1 to 8 hours. The reaction can be carried out in the absence of any catalyst, but in some instances, it is found desirable to employ a base catalyst such as a tertiary amine.- Similarly, solvents are not necessary for carrying out the reaction, but, if desired, inert solvents such as normally liquid hydrocarbons, chlorinated hydrocarbons and ethers can be used.

Among the azo compounds that can be used to practice this inventionare:

Azo benzene 4-dimethylamino azobenzene 4-nitroazobenzene 4,4'-dihydroxyazobenzene 2,2'-dimethylazobenzene 4,4'-dichloroazobenzene 4-acetamidoazobenzene Z-aminoazobenzene 3-arninoazobenzene 4-aminoazobenzene 4-amino-2,3 '-dirnethylazobenzene 4-amino-3,4'-dimethylazobenzene 4-amino-2,3 '-dimethylazobenzene 2,2'-diaminoazobenzene 2,4-diaminoazobenzene 4,4-diaminoazobenzene 4,4-diethoxyazobenzene 2,2-dihydroxyazobenzene 4,4-dimethylazobenzene 3,3 '-dimethylazobenzene 4,4'-diphenylazobenzene 2-hydroxyazobenzene S-hydroxyazobenzene 4-hydroxyazobenzene 3,3 '-dichloroazobenzene 2,4-dichloroazobenzene 3 ,3 -dibromoazobenzene 4,4-dibromoazobenzene 2,2'-dibromoazobenzene 2,4-dibromoazobenzene 3-chloroazobenzene 4-chloroazobenzene 3-bromoazobenzene 4-bromoazobenzene The following examples are illustrative of this invention:

Azohenzene (0.05 mole) .and diethyl phosphorothiolothionate (0.05 mole) were mixed and heated on the steam bath with stirring for 1 hour. The product is a viscous red oil 1 1.6206 After standing torseveral days, it crystallized into large prisms.

Example 2.-0,0 dimethyl S [1 (p-dimethylaminoiphenyl -2 -pher yl-.1 Jlydrazino] phosphorothiolothionate 5P(S )(OCH:1)2 ,This compound was prepared from 4-dimethylaminoazobenzene (0.1 mole) and dimethyl phosphorothiolothionate (0.1 mole) accordingto the procedure of Exmp e 1,-

Example. 3...;-0,0-diis0.propyl S- [2- p-nitrophenyl -1 phenylel .-hydrazin 01phosphorothiolothionate oNHneim -sP(s)[oH(oH3)z]z This compound-was prepared from 4-nitroazobenzene "(0.1 mole") and diisopropyl phosphorothiolothionate (0.1 mole) according to the procedure of Example 1.

Example ;4.--0,0-dierl yl 'S-[1,2 bis(p-hydroxypher yl)- hydrgzinoj pligsphorothiolothionate SP(S)(OC2H5)2' .Thiscompound was prepared from 4,4-dihydroxyazobenzene (0.1 mole) and diethyl phosphorothiolothionate (0.1 mole) according to the procedure of Example 1.

Example 5 .-0,0-diethyl S-[ 1, 2-bis,(o-tolyl)hydrazino1- phosphorothiolothionate CH3 CH3 This compound was prepared from 2,2-dimethylazobenzene (0.1 mole) and diethyl phosphorothiolothionate (0.1 mole) according to the'procedureof Example 1.

Example 6.0,0-diethyl S-E1,2-bis(p-chl0rophenyl)- hydrazino] phosphorothiolo thionate CL-Q-NlI-TQ-Cl SP(S)(QC2H5)2 This compound was prepared from 4,4'-dichloroaz obenzene (0.1 mole) and diethyl phosphorothiolothionate (0.1 mole) according to the procedure of Example 1.

Example 7.-Uti lity Tests against mites were carried out in the follow-ing manner. Acetone solutions containing 1% of the candidate compounds were prepared and diluted .with water to give solutions of the desired concentration for testing. Two heavily infested bean leaves containing adult twospotted mites (T etranychus bimaculatus Harvey) were carefully dipped in the above solutions and dried in a gentle air stream. The leaves were then placed on damp paper toweling in Petri dishes and observed after24 hours for mortality among the adult mites.

TABLE 1 [-Toxicant: 0,0;d-iethyl -S-(1,2-dipheny1hydrazino) phosphoro thiolothionate (Example 1).] .Gopssn retioninracm Per e kil mi e .f 77777-77377 737', 100 100 30 10 0 0 We claim: '1. The organophosphorus compounds having the :structural formula:

Ra GR;

2. 0,0 diethyl S -.(1,2 diphenylhydrazino)phosphorothiolothionate having the formula:

CaHsNHNCuHs SP(S)(QC2H)2 3. 0,0-dimethyl S- [.1 (p-dirnethylaminophenyl)-2-phen yl-l-hydrazino]phosphorothiolothionate having the for- 4, 0,0 d sopropy S (p n hsny phenyl 1 hydrazineJphosphorothiolothionate having the formula:

5. 0,0 diethyl S {1,2 bis(o tolyl)hydrazino]- phosphorothiolothionate having the formula:

6. 0,0 diethyl S [1,2 bis(p chlorophenylfi ydrazino]phosphorothiolothionate having the formula:

vou grm n 7. The method for producingorganophosphorus compounds which comprises reacting a dialkyl phosphorothiolothionate having the structural formula:

1120 wherein R and R are lower alkyl radicals containing 1 to 4 carbon atoms with an azo compound having the structural formula:

s liea eselra sd iramthe-gramme ting nine 'h s rpr Y a als h r snssh ari i re biiami s tyii taining 1 to 4 carbon atoms, phenyl and amido radicals having the formula i Ii NOR wherein R is an alkyl radical containing 1 to 4 carbon atoms at a temperature within the range of -25 to 150 C.

8. The method for producing 0,0-diethy1 S-(1,2-diphenylhydrazino)phosphorothiolothionate which comprises reacting diethyl phosphorothioiothionate with azobenzene at a temperature within the range of 25 to 150 C.

9. The method for producing 0,0-dimethy1 S-[l-(pdimethylaminophenyl) 2 phenyl 1 hydrazinoJphosphorothiolothionate which comprises reacting dimethyl with 4-dimethylaminoazobenzene at a temperature within the range of 25 to 150 C.

No references cited. 

1. THE ORGANOPHOSPHORUS COMPOUNDS HAVING THE STRUCTURAL FORMULA: 